201247802 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種被覆膜形成用組合物及被覆膜形成方 法、以及於表面形成有被覆膜之基體及其用途。 【先前技術】 知有於要求撥水性之各種基體表面燒附具有與發原子 鍵結之氫原子之有機聚石夕氧烧而形成疏水性被覆膜。 例如，於日本專利特開2000-119642號公報中揭示有一 種含有具有與矽原子鍵結之氫原子之有機聚矽氧烷的撥水 性被覆膜形成用組合物，於日本專利特開201 0-60162號公 報中揭示有一種具有包括冷卻片之熱交換器之熱泵式空氣 調節器’該冷卻片具有包含該組合物之撥水性被覆膜。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2000-119642號公報 [專利文獻2]曰本專利特開2010-60162號公報 【發明内容】 [發明所欲解決之問題] 然而’具有上述撥水性被覆膜之表面之疏水性不充分， 例如於表面具有上述撥水性被覆膜之冷卻片之情形時，若 不將冷卻片配置為接近垂直之角度，則附著於表面之水滴 難以滑落。於冷卻風扇上附著有水滴之狀態下，根據運轉 條件不同，於冷卻片表面產生霜，從而熱交換器中之通風 阻力增大’通風量降低’並且熱交換器之熱交換面中之空 163665.doc 201247802 氣側之熱傳遞性能降低，熱交換器之能力降低。 本發明之目的在於提供一種可形成具有較高之疏水性且 具有充分滑水性能之撥水性被覆膜的組合物及方法。又， 本發明之目的亦在於提供一種具有此種較高之疏水性之基 體’例如散熱體。 [解決問題之技術手段] 本發明之目的係藉由如下被覆膜形成用組合物而達成， 該被覆膜形成用組合物包含： (A) 有機烷氧基矽烷； (B) 含有與石夕原子鍵結之氫原子之有機聚矽氧烷；及 (C) 縮合反應觸媒。 作為上述（B)含有與矽原子鍵結之氫原子之有機聚矽氧 烧’較佳為下述平均單元式（1)所示者： [R1R2R3Si〇1/2]2[R4HSi02/2]m[R52si〇2/2]n [式中，R、R及R3分別獨立為一價烴基或氫原子，R4及 R5分別獨立為一價烴基’ 〇1為0或正數，n為正數，（m+n)之 值為5〜500’ {m/(m+n)}之值為〇〜〇3，其中於m>〇時末 端矽烷基之矽原子上所鍵結之氫原子為〇〜2個，於瓜=〇 時’末端石夕炫基之石夕原子上所鍵結之氮原子為W2個]。 於上述平均單元式（1)中，更佳為爪=0。 作為上述（C)縮合反應觸媒，較佳為辞、錫、猛、姑或 鐵系觸媒。 本發明之被覆膜形成用組合物令之上述（A)有機烧氧基 石夕院的調配量以組合物之全部固形物成分質量為基準計較 163665.doc -4- 201247802 佳為1〜90質量％之範圍。 本發明之被覆膜形成用組合物中之上述（B)含有與矽原 子鍵結之氫原子之有機聚矽氧烷的調配量以組合物之全部 固形物成分質量為基準計較佳為1〜9〇質量。/〇之範圍。 本發明之被覆膜形成用組合物中之上述（c)縮合反應觸 媒的調配量以組合物之全部固形物成分質量為基準計較佳 為0.001〜8質量％之範圍。 本發明之被覆膜形成用組合物較佳為進而包含（D)碎氧 樹脂。 作為上述（D)矽氧樹脂’較佳為下述平均單元式（2)所示 者： [R6Si〇3/2]a[R7R8pSiO(3-p)/2]b (2) {式中’ R6及R7分別獨立為一價烴基，R8分別獨立為燒氧 基或羥基’其中’ R8中之70莫耳％以上為烷氧基，p為 p<3之範圍之數，a為0或正數，b為正數，且0.5$b/(a+b)S 1.0}。 本發明之被覆膜形成用組合物亦可進而包含（E)石夕氮化 反應觸媒。 本發明亦關於一種將上述被覆膜形成用組合物應用於基 體表面後進行加熱之被覆膜形成方法。 上述基體表面較佳為包含無機材料。 上述基體表面亦可已包括含有石夕之被覆膜。 上述加熱可於100〜300°c之溫度範圍内進行。 本發明亦關於一種藉由上述被覆膜形成方法而於表面形 163665.doc 201247802 成有被覆膜之基體。 上述基體可於含有水蒸氣之氣體中較佳地使用》 上述基體可較佳地用於散熱體’又，上述基體或上述散 熱體可較佳地用於熱交換器。 [發明之效果] 本發明之被覆膜形成用組合物及被覆膜形成方法可形成 具有較尚之疏水性且具有充分滑水性能之撥水性被覆膜。 藉由本發明而獲得之被覆膜具有較高之疏水性，且可具 有如下優異之滑水性能：即便為如2 μΐ般之極少量之水 滴’亦僅藉由使被覆膜稍稍傾斜便可使附著於被覆膜上之 水滴滑落。例如，將上述傾斜角相對於水平面設為15度以 下。 又’由於本發明之基體具備具有較高之疏水性且具有充 分滑水性能之撥水性表面，故而適合作為於空氣中使用之 散熱體，尤其適於與外部空氣進行熱交換之熱交換器。 【實施方式】 本發明之被覆膜形成用組合物至少包含： (Α)有機坑氧基石夕烧； (Β)含有與矽原子鍵結之氫原子之有機聚矽氧烷；及 (C)縮合反應觸媒。 上述（Α)有機烷氧基矽烷係用以藉由與上述（β)含有與矽 原子鍵結之氫原子之有機聚矽氧烷併用而形成具有優異之 滑水特性之硬化被覆膜的成分。上述⑷有機烧氧基石夕烧 只要具有至少丨個與矽原子鍵結之有機基及至少丨個烷氧 163665.doc 201247802 基，則並無限定，較佳為下述通式：[Technical Field] The present invention relates to a coating film forming composition and a coating film forming method, and a substrate having a coating film formed on the surface thereof and use thereof. [Prior Art] It is known that an organic coating having a hydrogen atom bonded to an atom is burned on the surface of various substrates requiring water repellency to form a hydrophobic coating film. For example, Japanese Laid-Open Patent Publication No. 2000-119642 discloses a water-repellent coating film-forming composition containing an organic polyoxosiloxane having a hydrogen atom bonded to a ruthenium atom. A heat pump type air conditioner having a heat exchanger including a cooling fin having a water repellency coating film containing the composition is disclosed in Japanese Patent Publication No. 60162. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-119642 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-60162 (Invention) [Problems to be Solved by the Invention] However, when the surface of the water-repellent coating film is insufficient in hydrophobicity, for example, in the case of a cooling sheet having the water-repellent coating film on the surface, if the cooling sheet is not disposed at an angle close to a vertical direction, it adheres to Water droplets on the surface are difficult to slip. In the state where water droplets are attached to the cooling fan, frost is generated on the surface of the cooling fin depending on the operating conditions, so that the ventilation resistance in the heat exchanger is increased, 'the amount of ventilation is reduced' and the heat exchange surface of the heat exchanger is empty 163665 .doc 201247802 The heat transfer performance of the gas side is reduced and the capacity of the heat exchanger is reduced. SUMMARY OF THE INVENTION An object of the present invention is to provide a composition and method which can form a water-repellent coating film having high hydrophobicity and sufficient water-skiing properties. Further, it is an object of the present invention to provide a substrate having such a high hydrophobicity such as a heat sink. [Means for Solving the Problems] The object of the present invention is achieved by a composition for forming a coating film comprising: (A) an alkoxy decane; (B) containing a stone An organic polyoxane of a hydrogen atom bonded to the atom; and (C) a condensation reaction catalyst. As the above (B), the organopolyoxyl group containing a hydrogen atom bonded to a ruthenium atom is preferably represented by the following average unit formula (1): [R1R2R3Si〇1/2]2[R4HSi02/2]m [R52si〇2/2]n [wherein R, R and R3 are each independently a monovalent hydrocarbon group or a hydrogen atom, and R4 and R5 are each independently a monovalent hydrocarbon group' 〇1 is 0 or a positive number, n is a positive number, (m The value of +n) is 5~500' {m/(m+n)} is the value of 〇~〇3, where the hydrogen atom bonded to the 矽 atom of the terminal 矽alkyl group at m>〇 is 〇~2 In the case of melon = 〇, the nitrogen atom bound to the stone of the end of the Shi Xi Xuanji is W2]. In the above average unit formula (1), it is more preferable that the claw is =0. The (C) condensation reaction catalyst is preferably a rhenium, tin, turmeric, or an iron-based catalyst. In the composition for forming a coating film of the present invention, the amount of the above-mentioned (A) organic oxy- oxet compound is calculated based on the mass of all the solid components of the composition, 163665.doc -4- 201247802 preferably 1 to 90 mass The range of %. In the composition for forming a coating film of the present invention, the amount of the organopolysiloxane containing the hydrogen atom bonded to the ruthenium atom in the above (B) is preferably 1 to 1 based on the total mass of the solid content of the composition. 9 〇 quality. / Range of 〇. In the composition for forming a coating film of the present invention, the amount of the (c) condensation reaction catalyst is preferably in the range of 0.001 to 8 mass% based on the total mass of the solid content of the composition. The coating film-forming composition of the present invention preferably further comprises (D) a pulverized resin. The above (D) oxime resin is preferably the one represented by the following average unit formula (2): [R6Si〇3/2]a[R7R8pSiO(3-p)/2]b (2) {wherein' R6 and R7 are each independently a monovalent hydrocarbon group, and R8 is independently an alkoxy group or a hydroxyl group, wherein 70% or more of R8 is an alkoxy group, p is a number of p<3, and a is 0 or a positive number. , b is a positive number, and 0.5$b/(a+b)S 1.0}. The composition for forming a coating film of the present invention may further comprise (E) a catalytic reaction catalyst. Further, the present invention relates to a method for forming a coating film obtained by applying the composition for forming a coating film to a surface of a substrate and then heating the composition. The surface of the above substrate preferably contains an inorganic material. The surface of the above-mentioned substrate may also include a coating film containing Shi Xi. The above heating can be carried out at a temperature ranging from 100 to 300 °C. The present invention also relates to a substrate in which a coating film is formed on the surface shape 163665.doc 201247802 by the above-mentioned coating film forming method. The above substrate can be preferably used in a gas containing water vapor. The above substrate can be preferably used for a heat dissipating body. Further, the above substrate or the above-mentioned heat dissipating body can be preferably used for a heat exchanger. [Effects of the Invention] The coating film-forming composition and the coating film forming method of the present invention can form a water-repellent coating film having a relatively hydrophobic property and sufficient water-skiing performance. The coating film obtained by the present invention has high hydrophobicity and can have excellent water-skiing performance: even a very small amount of water droplets such as 2 μΐ can be only slightly tilted by the coating film. The water droplets attached to the coating film are slid down. For example, the above inclination angle is set to 15 degrees or less with respect to the horizontal plane. Further, since the substrate of the present invention has a water-repellent surface having high hydrophobicity and sufficient water-skiing property, it is suitable as a heat sink for use in air, and is particularly suitable for a heat exchanger for heat exchange with outside air. [Embodiment] The composition for forming a coating film of the present invention contains at least: (Α) an organic pit oxygen oxysulfide; (Β) an organopolysiloxane having a hydrogen atom bonded to a ruthenium atom; and (C) Condensation reaction catalyst. The above (Α) organoalkoxy decane is used to form a component of a hardened coating film having excellent water-skiing characteristics by being used in combination with the above (β) organic polyoxyalkylene having a hydrogen atom bonded to a ruthenium atom. . The above (4) organic alkoxylate is not limited as long as it has at least one organic group bonded to a ruthenium atom and at least one alkoxy 163665.doc 201247802, and is preferably a formula:
RaxSi(ORb)4.x 所不者。作為⑷有機炫氧基碎燒，可單獨使用1種 氧基石夕院…視需要亦可併用2種以上有機貌氧基石; 院。 上述通式中，R分別獨立表示一價烴基。作為一價庐 基，較佳為碳原子數卜3〇之經取代或未經取代之直鍵狀^ 为支狀之一價烴基，例如可列舉：甲基、乙基、丙基、丁 基、戍基、己基、庚基、辛基等碳原子數卜3 原子數1〜20、更佳為浐疮工如， 马及 . 更佳為妷原子數1〜6之直鏈狀或支鏈狀之烷 基環戊基、環己基等碳原子數3〜3()、較佳為碳原子數 3'!〇、更佳為碳原子數3〜6之環烷基；乙烯基、烯丙基、 丁烯基等碳原子數2〜30、較佳為碳原子數2〜20、更佳為碳 原子數w之直鍵狀或支鏈狀之稀基；笨基、甲笨基2 原：數6 30、較佳為碳原子數6〜2〇、更佳為碳原子數6〜1〇 之方基，¥基等碳數7〜30、較佳為碳原子數7〜2q、更佳為 碳原子數7〜1〇之芳烷基；以及與該等基之碳原子鍵結之氫 原子至少部分性地經氣等齒素原子取代之基。作為一價烴 基：較佳為碳原子數1〜6之直鏈狀之烷基、烯基或芳基， 進而更佳為甲基或乙基、乙烯基、苯基。 美丄述通式申’ Rb分別獨立表示甲基、乙基、丙基、丁 二:戊基、己基、庚基、辛基等碳原子數卜3〇、較佳為碳 ^數1 2G、更佳為碳原子數1〜6之直鏈狀或支鍵狀之烧 土 c作為Rb，較佳為曱基、乙基、丙基。 163665.doc 201247802 上述通式中，x為0〜3之整數，較佳為，更佳為1。 作為上述（A)有機院氧基石夕院，例如可列舉：甲基=甲 氧基矽烷'曱基三乙氧基矽烷、乙基三甲氡基矽烷、:基 二乙氧基矽烷、第三丁基三甲氧基矽烷、第三丁基三乙氧 基矽烷、正己基三曱氧基矽烷' 正己基三乙氧基矽烷、辛 基二曱氧基矽烷、辛基三乙氧基矽烷、癸基三甲氧基矽 烷、癸基二乙氧基矽烷 '二曱基二曱氧基矽烷二甲基二 乙氧基矽烷、第三丁基甲基二曱氧基矽烷、第三丁基曱基 二乙氧基矽烷、正己基甲基二曱氧基矽烷、正己基曱基二 乙氧基矽烷、辛基甲基二甲氧基矽烷、辛基甲基二乙氧基 矽烷、癸基甲基二甲氧基矽烷、癸基甲基二乙氧基矽烷、 乙烯基三曱氧基矽烷、烯丙基三曱氧基矽烷、烯丙基三乙 氧基矽烷、烯丙基三（乙氧基甲氧基）矽烷、丁烯基三曱氧 基矽烷 '己烯基三曱氧基矽烷、己烯基三乙氧基矽烷苯 基二甲氧基矽烷、苯基三乙氧基矽烷、甲基苯基二甲氧基 矽烷、甲基苯基二乙氧基矽烷、3,3,3_三氟丙基三甲氧基 矽烷、3,3,3-三氟丙基三乙氧基矽烷' 3,3,3_三氟丙基曱基 一甲氧基矽烷、3,3,3-三氟丙基▼基二乙氧基矽烷等。 關於本發明之被覆膜形成用組合物中之上述（八）有機烧 氧基矽烷之調配量，只要可形成撥水性被覆膜，則並無特 別限疋，以被覆膜形成用組合物之全部固形物成分質量為 基準計較佳為1〜90質量％，更佳為1〇〜85質量％ ’進而更佳 為30〜80質量％。 上述（B)含有與矽原子鍵結之氫原子之有機聚矽氧烷係 163665.doc 201247802 用以藉由與上述（A)有機烷氧基矽烷併用而形成具有優異 之滑水特性之硬化被覆膜的成分。含有與矽原子鍵結之氫 原子之有機聚矽氧烷只要具有至少丨個、較佳為至少2個與 矽原子鍵結之氫原子，則並無限定，可為具有直鏈狀、支 鏈狀、環狀、網狀之任一結構者，較佳為下述 ⑴所示之直鏈狀者： 式 中，R〗、R2及R3分別獨立為一價烴基或氫原子，Μ及 R5分別獨立為-價煙基，正數，n為正數，加+4之 值為5〜500’ {m/(m+n)}之值為。〜〇3，其中於時末 端梦院基之梦原子上所鍵結之氫原子為卜2個於㈣ 時末端矽烷基之矽原子上所鍵結之氫原子為1或2個]。 作為上，（B)含有與發原子鍵結之氩原子之有機聚石夕氧 二:可早獨使用1種含有與矽原子鍵結之氫原子之有機聚 石m X ’視需要亦可併用2種以上含有㈣原子鍵結 之紅原子之有機聚矽氧烷。 上述平均單元式⑴中之一價煙基之定義及例示如 述。作為一價炮其 n 土’較佳為碳原子數1〜6之直鍵狀之产 基、烯基或芳灵，、#芯 且越狀之烷 方基進而更佳為甲基或乙基、乙烯基、笨 ^述平均單元式⑴中，較佳為心/( Μ 而更佳為 於上述平均單开， 式（1)中，就被覆膜之厚度之調整容易 庄3面而言，較佳RaxSi(ORb)4.x is not. As the (4) organic oxy-oxyl calcination, one type of Oxygen Stone Garden can be used alone, and two or more kinds of organic oxy-stones can be used in combination as needed; In the above formula, R each independently represents a monovalent hydrocarbon group. The monovalent fluorenyl group is preferably a substituted or unsubstituted straight-chain hydrocarbon group having a carbon number of 3 Å, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. , fluorenyl, hexyl, heptyl, octyl and other carbon atoms, 3 atoms, 1 to 20, more preferably hemorrhoids, horses and horses. More preferably a linear or branched chain of 1 to 6 atoms. The alkylcyclopentyl group, the cyclohexyl group and the like have 3 to 3 (3) carbon atoms, preferably 3'!, more preferably a cycloalkyl group having 3 to 6 carbon atoms; vinyl or allylic group a base or a butenyl group having a carbon atom number of 2 to 30, preferably a carbon number of 2 to 20, more preferably a direct bond or a branched chain of a carbon atom; a number of 6 30, preferably 6 to 2 Å, more preferably 6 to 1 Å, and a carbon number of 7 to 30, preferably 7 to 2 q, more preferably Preferably, the aralkyl group having a carbon number of 7 to 1 Å; and a hydrogen atom bonded to a carbon atom of the group are at least partially substituted with a dentate atom such as a gas. The monovalent hydrocarbon group is preferably a linear alkyl group, an alkenyl group or an aryl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a vinyl group or a phenyl group. The general formula "Rb" independently represents a methyl group, an ethyl group, a propyl group, a butyl group: a pentyl group, a hexyl group, a heptyl group, an octyl group, etc., and a carbon number of 3 Å, preferably a carbon number of 1 2 G, More preferably, it is a linear or branched burnt clay c having a carbon number of 1 to 6 as Rb, preferably a mercapto group, an ethyl group or a propyl group. 163665.doc 201247802 In the above formula, x is an integer of 0 to 3, preferably, more preferably 1. Examples of the above-mentioned (A) organic compound oxygen stone court include methyl group = methoxydecane 'mercapto triethoxy decane, ethyl trimethyl decyl decane, dimethyl dimethoxy decane, and third butyl group. Trimethoxy decane, tert-butyltriethoxy decane, n-hexyl decyloxydecane 'n-hexyl triethoxy decane, octyl decyloxydecane, octyl triethoxy decane, fluorenyl Trimethoxy decane, decyl diethoxy decane 'didecyl decyloxydecane dimethyl diethoxy decane, tert-butyl methyl decyl decane, tert-butyl decyl diethoxy Decane, n-hexylmethyldimethoxydecane, n-hexyldecyldiethoxydecane, octylmethyldimethoxydecane, octylmethyldiethoxydecane, decylmethyldimethoxy Decane, mercaptomethyldiethoxydecane, vinyl trimethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, allyl tris (ethoxy methoxy) Decane, butenyl trimethoxy decane 'hexenyl trimethoxy decane, hexenyl triethoxy decyl phenyl dimethoxy decane, benzene Triethoxydecane, methylphenyldimethoxydecane, methylphenyldiethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropane Triethoxy decane '3,3,3-trifluoropropyl decyl monomethoxy decane, 3,3,3-trifluoropropyl ▼ bis ethoxy decane, and the like. The compounding amount of the above (8) organic alkoxy decane in the coating film-forming composition of the present invention is not particularly limited as long as the water-repellent coating film can be formed, and the coating film-forming composition is used. The mass of all the solid components is preferably from 1 to 90% by mass, more preferably from 1 to 85% by mass, and still more preferably from 30 to 80% by mass. The above (B) an organopolyoxyalkylene system containing a hydrogen atom bonded to a ruthenium atom 163665.doc 201247802 is used to form a hardened water having excellent water-skiing characteristics by being used in combination with the above (A) organoalkoxydecane. The composition of the film. The organopolysiloxane having a hydrogen atom bonded to a ruthenium atom is not limited as long as it has at least one, preferably at least two, hydrogen atoms bonded to a ruthenium atom, and may have a linear or branched chain. Any one of a shape, a ring shape and a mesh shape is preferably a linear one represented by the following (1): wherein R, R2 and R3 are each independently a monovalent hydrocarbon group or a hydrogen atom, and Μ and R5 are respectively Independently for the price of the smoke base, positive number, n is a positive number, plus the value of +4 is 5~500' {m/(m+n)}. ~ 〇 3, in which the hydrogen atom bonded to the atom at the end of the dream is 2 or (2), and the hydrogen atom bonded to the argon atom of the terminal decyl group is 1 or 2]. As above, (B) an organic polyoxo-oxide containing an argon atom bonded to an atom; an organic polymethane containing a hydrogen atom bonded to a ruthenium atom may be used alone as needed. Two or more organic polyoxoxanes containing a (four) atom-bonded red atom. The definition and exemplification of one of the above-mentioned average unit formulas (1) is as follows. As a monovalent gun, its n soil 'is preferably a direct bond-like base of a carbon atom number of 1 to 6, an alkenyl group or an aromatic group, a # core and an alkyl group which is more like a methyl group or an ethyl group. In the average unit type (1), it is preferably a core/( Μ and more preferably an average single opening, and in the formula (1), the thickness of the coating is easily adjusted. Better
馬5客m+n $ 400，更佳為8 S m+n S 163665.doc 201247802 300，進而更佳為10$m+nS 200。 作為上述（B)成分’較佳為分子鏈兩末端由二烷基氫石夕 炫氧基封閉之一烧基聚石夕氧烧或分子鍵單末端由二烧美氮 矽烷氧基封閉之二烷基聚矽氧烷。因此，於上述平均單元 式（1)中較佳為m=0。 關於本發明之被覆膜形成用組合物中之上述（B)含有與 石夕原子鍵結之氫原子之有機聚矽氧烷的調配量，只要可形 成撥水性被覆膜，則並無特別限定，以被覆膜形成用組合 物之全部固形物成分質量為基準計較佳為丨〜卯質量％，更 佳為2〜70質量％，進而更佳為5〜50質量％。其中，於以在 撥水性被覆膜之表面存在聚矽氧油為不佳之情形時，上述 (B)含有與矽原子鍵結之氫原子之有機聚矽氧烷的調配量 以被覆膜形成用組合物之全部固形物成分質量為基準計較 佳為1〜1 5質量％，更佳為1〜1 〇質量〇/〇。 上述（C)縮合反應觸媒係用以使上述（A)有機烷氧基矽烷 與上述（B)含有與矽原子鍵結之氫原子之有機聚矽氧烷進 行縮合反應而形成硬化被覆膜的觸媒。上述縮合反應係 (A) 有機烷氧基矽烷中之烷氧基水解而產生之矽烷醇基與 (B) 含有與矽原子鍵結之氫原子之有機聚矽氧烷中之與矽 原子鍵結之氫原子之間的縮合反應。作為上述（c)縮合反 應觸媒，可單獨使用1種縮合反應觸媒，又，視需要亦可 併用2種以上縮合反應觸媒。 關於上述（C)縮合反應觸媒之種類，只要可形成硬化被 覆膜，則並無限；t。作為上述（c)縮合反應_，例如可 163665.doc •10· 201247802 使用鋅m或鐵系觸媒。作為鋅、錫、猛、姑或 鐵系觸媒，較佳為有機酸金屬鹽，作為有機酸，較佳為脂 肪酸。作為上述(C)硬化_，具體而言，例如可列舉： 二乙酸鋅、二辛酸辞、辛酸鋅、二新癸酸鋅、雙十一碳烯 酸鋅、二曱基丙稀酸鋅；二新癸酸二f基錫、=乙酸二丁 基錫、二辛酸二丁基錫、二月桂酸二丁基錫、二月桂酸二 辛基錫、二油酸二丁基錫、二甲氧基二丁基錫、二辛酸 錫—月桂酸錫、一乙酸錫、四乙酸錫、氧化二丁基錫、 节基順丁烯二酸二丁基錫、雙（三乙氧基矽烷氧基）二丁基 錫、二乙酸二苯基錫、辛酸錫、新癸酸二曱基錫；二乙酸 猛一辛酸猛、辛酸猛；二乙酸銘、二辛酸钻、辛酸銘； 二乙酸鐵、二辛酸鐵及辛酸鐵等。 本發明之被覆膜形成用組合物中之上述（c)縮合反應觸 媒之調配量並無限定’以被覆膜形成用組合物之全部固形 物成分質量為基準計較佳為0.01〜8質量％，更佳為〇質 量0/。，進而更佳為1〜3質量％。 本發明之被覆膜形成用組合物較佳為進而包含（D)矽氧 樹脂。包含上述（D)矽氧樹脂之本發明之被覆膜形成用組 合物可形成厚度更均勻且緻密之被覆膜。因此，包含上述 (D)矽氧樹脂之部分水解縮合物之本發明之被覆膜形成用 组合物可形成就防銹性等方面而言更優異之被覆膜。 作為上述（D)矽氧樹脂，可例示：包含單元式（Resi〇3/2) 所示之三官能性矽氧烷單元（以下記作T單元）、視需要之 單元式（Re2Si02/2)所示之二官能性矽氧烷單元（以下記作d 163665.doc 201247802 單兀）及單元式（R^SiOm)所示之單官能性矽氧烷單元（乂 下記作Μ單元）的DT型或MDT型矽氧樹脂；包含單元 (siOw)所示之四官能性矽氧烷單元（以下記作q單元= 單元的MQ樹脂。上式中，RC分別獨立表示一價煙基。^ 為：價烴基’可例示㈣相同之基…少量之“可為 〇Rb所示之烷氧基或羥基(D)矽氧樹脂於常溫下可為固體 狀亦可為液狀’於為固體狀之情形時，亦可具有炫點。 其中，較佳為下述平均單元式（2)所示者· [R Sl〇3/2]a[R7R8pSi〇(3.p)/2]b (2) {式中’ R及R分別獨立為一價烴基，尺8分別獨立為烷氧 基或經基，其中，R8中之7〇莫耳％以上為貌氧基p為Μ Ρ<3之範圍之數，a為G或正數，b為正數，且化b/(a+b^ 1.0} » 上述（D)平均單疋式（2)所示之#氧樹脂較佳為有機燒氧 基石夕炫之部分水解縮合物，只要為具有龍氧基之 有機烧氧基錢之部分水解縮合物，則並無限定。作為有 機烷氧基矽烷之部分水解縮合物，可單獨使用1種有機烷 U Μ 刀水解縮合物’又’視需要亦可併用2種以 上有機烧氧基碎炫之部分水解縮合物。 上述平均單元式（2)中之一價煙基之定義及例示如上所 述。作為-價烴基，較佳為碳原子數卜6之直键狀之坑 基'烯基或芳基’進而更佳為甲基或乙基、乙稀基、苯 基》 上述（D)矽氧樹脂較佳 為於1分子中具有至少1個烯基 16366S.doc -12, 201247802 作為該情形時之烯基，較佳為乙烯基。 上述平均單元式（2)中之烷氧基為碳原子數丨〜” ' 較佳 為碳原子數1〜20、更佳為碳原子數1〜6之直鏈狀之烷氧 基，具體而言，可列舉甲氧基、乙氧基、丙氧基等。更佳 為曱氧基或乙氧基，進而更佳為甲氧基。 於上述平均單元式（2)中，較佳為3 $ a+b S 1 〇〇，更佳為 4ga+b^50,進而更佳為 5^a+b^2〇。 本發明之被覆膜形成用組合物中之上述（D)矽氧樹脂的 調配量並無限定，以被覆膜形成用組合物之全部固形物成 分質量為基準計較佳為5〜80質量％，更佳為10〜50質量％， 進而更佳為15〜43質量％。 本發明之被覆膜形成用組合物亦可進而包含（E)矽氫化 反應觸媒。尤其於本發明之被覆膜形成用組合物包含上述 (D)矽氧樹脂之情形時，且尤其於上述（D)矽氧樹脂含有烯 基之情形時，較佳為進而包含（£)矽氫化反應觸媒。作為 上述（E)矽氫化反應觸媒，可單獨使用丨種矽氫化反應觸 媒，又，視需要亦可併用2種以上矽氫化反應觸媒。 作為上述（E)矽氫化反應觸媒，可使用作為矽氫化觸媒 公知者，例如鉑、釕、鍺、鈀、餓、銥等化合物。尤其鉑 系觸媒較有用。作為鉑系觸媒之例，可使用氣鉑酸、鉑之 單體、將固體鉑擔載於氧化鋁、二氧化矽、碳黑等載體 者、鉑-乙烯基矽氧烷錯合物、鉑_膦錯合物、鉑_亞磷酸酯 錯合物、醇鉑觸媒等。於進行矽氫化反應時，鉑系觸媒以 鉑計，可使用以被覆膜形成用組合物之全部固形物成分質 163665.doc •13· 201247802 量為基準計為〇.〇〇〇〇1質量％〜〇」質量％左右。 本發明之被覆膜形成用組合物例如可藉由將上述 (A)〜（C)成分、以及視需要之上述（D)及/或（E)成分、進而 其他任意成分與溶劑混合而製備。 作為任意成分’只要為不妨礙所獲得之撥水性被覆膜之 效果的添加劑，則其種類並無特別限定，例如可列舉：顏 料、染料、防腐劑、殺菌劑、抗老化劑、防蝕劑、防銹 劑、抗靜電劑、阻燃劑、防污劑等。 作為溶劑，可列舉：苯、曱苯、二曱苯等芳香族烴化合 物’二乙&$、二異丙醚、四氫咬喃等喊化合物；甲醇、乙 醇、丙醇、丁醇、己醇等醇化合物；丙酮、甲基乙基酮、 曱基異丁基酮等酮化合物；乙酸乙酯、乙酸丁酯等酯化合 物；氣仿、三氣乙烯、四氣化碳等函化烴化合物；正己 烷、正辛烷、異辛烷、十八烷等飽和烴化合物；三曱基甲 氧基矽烷、二曱基二甲氧基矽烷、甲基三曱氧基矽烷四 乙氧基矽烷等矽烷化合物；六曱基二矽氧烷等揮發性聚矽 氧化合物等，但並不限定於該等。又，溶劑可單獨使用， 或亦可併用兩種以上。 本發明之被覆膜形成用組合物中之溶劑的調配量並無限 定，以被覆膜形成用組合物之全部質量為基準計較佳為 50 98質量％，更佳為7〇〜95質量％，進而更佳為〜列質量 %。換言之，本發明之被覆膜形成用組合物中之固形物成 刀里以被覆膜形成用組合物之全部質量為基準計較佳為 2〜50質量。/〇，更佳為5〜3〇質量％，進而更佳為〜質量 163665.doc 201247802 %» 本發明之被覆膜形成用組合物可藉由加熱使其硬化而形 成撥水性之被覆膜。因此，於本發明之被覆膜形成方法 中，藉由將上述被覆膜形成用組合物應用於基體表面後進 行加熱，而形成具有較高之疏水性且具有充分滑水性能之 撥水性被覆膜。 上述基體之材質為任意，可為金屬、金屬氧化物、玻 璃、陶瓷、塑膠、橡膠等，但就耐熱性方面而言，較佳為 至少基體表面（較佳為整個基體）包含金屬、金屬氧化物、 玻璃及陶瓷等無機材料。作為金屬，例如可列舉：鐵、 鋁、銅、金、銀、黃銅、錫、鎳及不鏽鋼等。再者，亦可 對金屬表面施加各種鑛敷。 上述基體表面亦可已包括含有矽之被覆膜。作為含有矽 之被覆膜’較佳為聚矽氧硬化被覆膜。 上述聚矽氧硬化被覆膜可藉由縮合反應硬化型、矽氫化 反應硬化型、有機過氧化物硬化型及紫外線硬化型等公知 之硬化機制而獲得。 縮合反應硬化型之聚矽氧硬化被覆膜例如可藉由使包含 以下各者之硬化性聚矽氧組合物硬化而獲得： (1)常溫下為液狀且分子鏈末端由矽烷醇基或與矽原子 鍵結之水解性基封閉之二有機聚矽氧烷、或具有與矽原子 鍵結之水解性基之有機矽烷之部分水解縮合物、 ⑺足以交聯⑴成分之量之具有與㈣子鍵結之水解性 基的有機矽烷系或有機矽氧烷系交聯劑、及 I63665.doc 15· 201247802 (3)所需量之縮合反應促進觸媒β 作為（1)成分中之與梦原子鍵結之水解性基，可例示： 一甲基酮肟基、甲基乙基酮肟基等酮肟基（ket〇xim〇)[有時 亦稱為酮肟基（ketoximino)，且為通式：_〇_n=cr9rig所示 之基（式中，R9及Ri〇為相同或不同之烷基，較佳為碳原子 數1〜6之烷基）];子氧基、乙氧基等烷氧基；乙醯氧基等 醯氧基；N-丁基胺基、N，N_二乙基胺基等烷基胺基；ν·甲 基乙醯胺基等醯胺基；Ν，Ν_二乙基胺氧基等Ν，Ν-二烷基胺 氧基；丙料基㈣氧基。於該〇較佳為絲基及嗣肪 基0 作為⑴成分，具體而言，可例示：分子鍵兩末端由石夕 烷醇基、與矽原子鍵結之甲氧基或乙氧基封閉之二甲基聚 矽氧烷、甲基烷基聚矽氧烷、二甲基矽氧烷-甲基苯基矽 氧烧，、聚物曱基（3,3,3·三氣丙基）聚石夕氧烧或烧氧基石夕烧 之=分水解縮合物等’但就硬化物之性狀及經濟性之方面 而。較佳為—甲基聚矽氧烷或烷氧基矽烷之部分水解縮 。物。再者為由與矽原子鍵結之曱氧基或乙氧基封閉 之-甲基聚矽氧烷之末端基，可例示：甲基二曱氧基矽烷 氧基 '甲基二乙氧基石夕炫氧基、三甲氧基石夕烧氧基、三乙 氧基我氧基、？基：甲氧基㈣基乙基（：甲基）錢氧 基、二曱氧基矽烷基乙基（二甲基）矽烷氧基等。 作為⑴成分，亦可併用2種以上二有機聚石夕氧烧或有機 石夕炫之。卩分水解縮合物。例如可列舉（丨⑴饥下之黏 2〇〜1〇〇ηΐΡ"之分子鏈兩末端由錢醇基封閉之二甲^聚 163665.doc •16· 201247802 矽氧烷、與〇2)25C下之黏度為looo〜5〇〇〇 mpa s之分子 鍵兩末端由石夕院醇基封閉之二甲基聚石夕氧院之混合物。此 處，成分（M)與成分（1-2)之調配比較佳為以質量比計處於 ⑽〜之卜於該情形時，成分⑴之黏度為不足 1000〜不足5000 mPa . s，塗佈性良好。 (2)成分為（1)成分之交聯劑，具有至少2個與矽原子鍵結 之水解性基，較佳為具有3個或4個與矽原子鍵結之水解性 基。具代表性的為通式：RnySiX4_y所示（式中，r11為碳原 子數1〜10之一仏烴基，X為與矽原子鍵結之水解性基，y為 0或1)之有機矽烧或作為該有機矽烧之部分水解縮合物之 有機矽氧烷低聚物。再者，一價烴基及與矽原子鍵結之水 解性基之定義及例示如上所述。 作為（2)成分，例如可例示：四曱氧基矽烷、四乙氧基 矽烷、正矽酸正丙酯、甲基三曱氧基矽烷、曱基三乙氧基 矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、乙烯 基二甲氧基矽烷、乙烯基三（2_甲氧基乙氧基）矽烷、夂胺 基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基 石夕烧、雙-[3-(二乙氧基石夕烧基）_丙基]四硫鍵、雙-[3_(三乙 氧基矽烷基）-丙基]二硫醚、甲基丙烯酸三乙氧基矽烷基丙 酯單硫醚、四（曱基乙基酮肟）矽烷、甲基三（甲基乙基酮 肟）矽烷、乙烯基三（甲基乙基酮肟）矽烷、曱基三乙醯氧基 矽烷、乙基三乙醯氧基矽烷、甲基三異丙烯氧基矽烷四 異丙烯氧基矽烷、甲基三（N，N_二乙胺基）矽烷。 (2)成分之調配量為足以使（丨）成分硬化之量，於硬化性 163665.doc： •17- 201247802 聚石夕氧組合物為單液型之情形時，為可在阻斷濕氣下長時 間保存、且當暴露於濕氣中時可於常溫下硬化之量，通常 為2〜30質量。/。之範圍。具體而言，（2)成分之調配量例如相 對於（1)成分丨〇〇質量份，為5〜1〇〇質量份’就硬化性方面 而& ’較佳為8〜40質量份之範圍。 作為（3)成为，可使用先前公知之縮合反應促進觸媒。 作為具體例，可列舉）乙酸二丁基錫、二辛酸二丁基 錫' 二月桂m二順丁稀二酸二丁基錫、二月桂 酸二辛基錫、二順丁烯二酸二辛基錫、辛酸錫等有機錫化 合物；鈦酸四（異丙基）酯' 鈦酸四（正丁基）酯、二丁氧基 雙（乙醯丙酮）鈦、三異硬脂醞基鈦酸異丙酯、三（二辛基焦 填酿氧基）欽酸異丙醋、雙（二辛基焦峨醢氧基）經乙酸欽酸 酯等有機鈦酸酯化合物；鍅酸四丁酯、四（乙醯丙酮）錯、 鍅i四異丁g曰、丁氧基二（乙醯丙酮）鍅、環烷酸鍅等有機 錄化。物，二（乙基乙酿乙酸）紹、三（乙g篮丙酮）紹等有機 銘化合物；環院酸鋅、環烧酸姑 '辛酸料有機酸金屬 | -乙醇胺、二乙醇胺等胺系觸媒。再者，有機錫化合 物或有機㈣g旨化合物適於脫醇型之縮合反應硬化性聚石夕 氧組合物，有機鈦酸醋化合物適於脫肟型之縮合反應硬化 性聚♦氧組合物。 (3)成分之調配量為足以促進⑴成分及⑺成分之縮合反 應之量，例如為G,1〜15質量％，較佳為卜㈣量％。若以⑴ 成分為基準’則例如相對於⑴成分1G0質量份，為(U〜2〇 質量份，就硬化性方面而言，較佳為丨〜12質量份之範圍。 163665.doc 201247802 夕氫化反應硬化型之聚哿氧硬化被覆膜例如可藉由對如 下硬化r生聚石夕氧組合物進行加熱硬化而獲得：&含1分子 中，、有至乂 2個與石夕原子鍵結之稀基之二有冑聚石夕氧烧（例 如，兩末端由二甲基乙稀基石夕烧氧基封閉之二甲基聚石夕氧 '元）刀子中具有至少2個、較佳為3個以上與石夕原子鍵 氫原子之有機聚矽氧烷（例如，兩末端由三甲基矽烷 氧基封閉之甲基氫聚石夕氧炫），石夕氫化反應觸媒（例如氣始 馱）以及較佳為進而包含矽氫化反應抑制劑。 為機過氧化物硬化型之聚發氧硬化被覆膜例如可藉由對 匕s 1刀子中具有至少2個烯基之二有機聚矽氧烷及有機過 氧ί匕物等的硬化性聚⑪氧組合物進行加熱硬化而獲得。 紫外線硬化型之聚矽氧硬化被覆膜例如可藉由使如下硬 化性聚矽氧組合物硬化而獲得：包含⑷矽氫化反應硬化型 有機聚吩氧;^及光聚合起始劑、（b)丙稀酸官能性聚石夕氧炫 及光聚合起始劑、或⑷環氧官能性有機料氧院及陽離子 產生型觸媒。 光聚合起始劑可自先前作為藉由照射紫外線而產生自由 基之化合物公知者，例如有機過氧化物 '羰基化合物、有 機硫化合物、偶氮化合物等中適當選擇。又，陽離子產生 型觸媒可自公知之鑌鹽，具體而言為三芳基疏鹽、三芳基 鎭鹽、雙（十二烷基苯基）六氟銻酸鹽等中適當選擇。 上述紫外線硬化型之硬化性聚矽氧組合物若於〇〜8〇它左 =之溫度下照射如下紫外線，則可形成硬化被覆膜，上述 紫外線之波長區域較佳為細〜彻nm、尤其於使用陽離子 163665.doc -19· 201247802 產生型觸媒之情形時更佳為200〜300 nm之範圍，又，於使 用石夕氫化反應硬化型有機聚矽氧烷之情形時較佳為 300〜400 nm之範圍。 本發明之被覆膜形成用組合物於基體表面之應用可利用 任意方法實施。作為應用方法，可利用浸潰塗佈'含浸 法、輥塗法、流塗法、刷塗法、喷霧法等。形成於基體表 面之被覆膜之厚度並無特別限定，但就導熱性方面而言’ 較佳為0.1〜5.0 μηι之厚度’更佳為丨〇〜2 μπΐ2厚度。 上述加熱例如可於100〜30〇t之溫度範圍内進行較佳 為120~250°C之溫度範圍，更佳為13〇〜2〇〇〇c之溫度範圍。 加熱時間並無限定，例如可於i分鐘〜丨小時之時間範圍内 加熱。較佳為於加熱前將塗佈有被覆膜形成用組合物之基 體放置於40 C以下之溫度、較佳為室溫下，使溶劑揮發。 [產業上之可利用性] 本發明之被覆膜形成用組合物及被覆膜形成方法可較佳 地用於要求優異撥水性之各種基體，例如可用於在含有水 蒸氣之氣體中使用且具備有結露及/或結霜之可能性之表 面的任意基體之表面處理。作為此種基體，例如可列舉廚 房、盥洗室、浴室等所謂用水場所製品。 由於本發明之基體具備具有較高之疏水性且具有充分滑 水性能之撥水性表面，故而可較佳地用於與外部空氣進行 熱父換之熱父換器，具體而言可用作散熱體。尤佳為使用 本發明之基體作為包括以固定間隔平行地設置之複數個冷 卻片、及連接該冷卻片之熱交換管之熱交換器的冷卻片。 I63665.doc -20- 201247802 並且，上述熱交換器更佳為具有 氣之送風機。 ° 7卹片輪送熱交換用空 本發明尤其可較佳地用 箱等冷凍裝置或冷藏裝置 ;在a有濕氣之環境中使用之冰 、空調等空氣調節裝置。 實施你】 丞於貫狍例及比較例對.双。。 ,. 本發明進行詳細說明，但 本發明並不受實施例限定。再者， 从t y 寄實施例及比較例中之滾 落角係以下述方式進行敎以及評價又甲基三甲氧基 矽烷部分水解縮合物丨及2係以下述方式進行土 [滚落角（滑落角）] 使用接觸角計（協和界面科學製造，DM_7〇〇)並利用滑落 法進行駭。具體而言’附液滴2 μ1之水，—面使附液滴 面傾斜，-面利用相機觀察水滴，將水滴之前端點及後端 點之兩者開始移動之瞬間的傾斜角度作為滾落角（滑落 角）〇 [曱基三甲氧基矽烷部分水解縮合物1之製備] 向設置有攪拌裝置、冷卻管及溫度計之5〇〇 ml之四口燒 瓶内投入曱基三曱氧基矽烷259.6 g、甲醇28.6 g及三氟甲 項酸0.13 g ’均勻混合後，滴下水29.6 g，於曱醇回流溫度 下使其反應1小時，於常壓下以120eC之溫度一面除去甲醇 一面使其反應3小時。冷卻至室溫後，吹入氨氣進行中 和，進而’於80°C之溫度及5〇 mmHg之減壓下進行汽提 後，實施過濾而獲得甲基三曱氧基矽烷部分水解縮合物 i。由13C NMR及29Si NMR之測定結果確認到所獲得之甲 163665.doc -21 · 201247802 基二甲氧基;ε夕烷部分水解縮合物1具有下述平均組成式β [CH3Si03/2]3 8[CH3R3丨 3Si〇丨 7/山 5 (式中，R3為甲氧基）。 [甲基三甲氧基矽烷部分水解縮合物2之製備] 向設置有擾拌聚置、冷卻管及溫度計之5〇〇 mi之四口燒 瓶内投入曱基三曱氧基矽烷265 1 g、曱醇23 3 g及三氟甲 績酸0.13 g ’均勻混合後，滴下水24 9 g，於曱醇回流溫度 下使其反應1小時，於常壓下以12〇eC之溫度一面除去甲醇 一面使其反應3小時。冷卻至室溫後，吹入氨氣進行中 和’進而於80°C之溫度及50 mmHg之減壓下進行汽提後， 實施過濾而獲得曱基三曱氧基矽烷部分水解縮合物2。由 13C NMR及29Si NMR之測定結果確認到所獲得之甲基三甲 氧基矽烷部分水解縮合物2具有下述平均組成式。 [CH3Si〇3/2]〇.3[CH3R3i.3Si017/2]3.0 (式中，R3為甲氧基）。 [實施例1〜16、比較例1〜2] 以表1〜3所記載之質量份數將表1〜3所示之成分均勻地混 合’而製備實施例1〜14及比較例1〜2之被覆膜形成用組合 物。再者，始系觸媒係以鉑金屬量為被覆膜形成用組合物 之固形物成分之10 ppm之方式進行調配。繼而，將浸潰於 驗性脫脂劑中進行脫脂處理後，利用流水及蒸餾水清洗並 進行加熱乾燥之鋁測試面板（ΠS A1050P)浸潰於上述組合 物中，並進行提拉’藉此以被覆膜形成用組合物被覆上述 測試面板表面。於室溫下將上述被覆測試面板放置數分 163665.doc -22· 201247802 鐘’使異辛烷揮發後’於2〇〇°c下加熱20分鐘，而於上述 測試面板表面上形成疏水性硬化被覆膜。 測定如此獲得之疏水性硬化被覆膜上之滾落角（滑落 角）。將結果一併示於表1〜3。 表中之MH、D之含義如下所述。 MH :表示（H(CH3)2Si〇1/2)單元 D·表示（(CHshSiO2,2)單元’下標表示£>單元之平均鍵數 又’表中之矽酸甲酯係三菱化學公司製造之製品名MKC Silicate MS56(—分子中之矽原子數平均為約1〇個）。又， 表中之MQ樹脂為下述平均單元式： [(CH3)3 Si〇i/2] 0.44 [Si〇4/2] 0.56 所示之矽氧樹脂，藉由凝膠滲透層析法所得之標準聚笨乙 烯換算之重量平均分子量為約4,600，含有約3重量❶/。之羥 基。 I:表 1] 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 實施 例7 甲基三甲氧基石夕烷 5.83 6.90 5.60 4.50 4.20 5.60 5.83 0.34 0.67 0.67 0.67 0.67 0.67 0.34 甲基三甲氧基矽烷 部分水解縮合物1 2.91 1.50 2.80 3.90 4.20 2.80 矽酸甲酯 - - - - 2.91 新癸酸二甲基錫 「0.18 0.18 0.18 0.18 0.18 0.18 「0.18 異辛烷 91 91 91 91 91 91 91 滾落角(滑落角） 5 5 5 7 13 5 6 163665.doc •23- 201247802 [表2] 實施例 8 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 甲基三甲氧基矽烷 - - 7.89 5.71 3.81 3.81 乙烯基三甲氧基矽烷 5.60 5.52 - - - - MmD98Mh 0.67 1.18 1.18 3.36 3.36 3.36 甲基三曱氧基矽烷部 分水解縮合物1 2.80 2.37 - - 1.90 - MQ樹脂 - - - - - 1.90 新癸酸二甲基錫 0.18 0.18 0.18 0.18 0.18 0.18 鉑系觸媒 10 ppm - - - 麵 異辛烷 91 91 91 91 91 91 滾落角（滑落角） 6 6 6 4 5 15 [表3] 實施例14 實施例15 實施例16 比較例1 比較例2 甲基三曱氧基矽烷 5.60 5.26 3.95 - - 乙烯基三曱氧基矽烷 5.60 5.52 - - - mhd98mh 0.67 1.18 1.18 0.67 0.67 曱基三甲氧基矽烷部 分水解縮合物1 - - 論 8.40 7.89 曱基三曱氧基矽烷部 分水解縮合物2 2.80 2.63 3.95 - - 新癸酸二甲基錫 0.18 0.18 0.18 0.18 0.18 異辛烷 91 91 91 91 91 滾落角（滑落角） 4 4 4 33 18 根據實施例1〜14及比較例1〜2之結果可知，本發明之被 覆膜形成組合物可形成具有良好滑水性能之撥水性硬化被 覆膜，另一方面，於不存在有機烷氧基矽烷時，所獲得之 硬化被覆膜之撥水性降低且滑水性變差。 163665.doc 24-The horse 5 is m+n $400, more preferably 8 S m+n S 163665.doc 201247802 300, and even more preferably 10$m+nS 200. As the above component (B), it is preferred that the two ends of the molecular chain are blocked by a dialkylhydrogen oxime oxy-oxygen group, and one of the single ends of the molecular chain is blocked by a di-s-azapine alkoxy group. Alkyl polyoxane. Therefore, m = 0 is preferable in the above average unit formula (1). In the composition for forming a coating film of the present invention, the amount of the organopolyoxane containing the hydrogen atom bonded to the cerium atom in the above (B) is not particularly limited as long as the water repellency coating film can be formed. The amount is preferably from 丨 to 卯% by mass, more preferably from 2 to 70% by mass, even more preferably from 5 to 50% by mass, based on the total mass of the solid content of the composition for forming a coating film. In the case where polyoxyphthalic acid is present on the surface of the water-repellent coating film, the amount of the organic polyoxane containing the hydrogen atom bonded to the ruthenium atom is formed by the coating film. It is preferably from 1 to 15% by mass, more preferably from 1 to 1% by mass based on the mass of the total solid content of the composition. The (C) condensation reaction catalyst is used to form a hardened coating film by subjecting the above (A) organoalkoxydecane to the above (B) organic polyoxyalkylene containing a hydrogen atom bonded to a ruthenium atom. Catalyst. The condensation reaction is carried out by (A) a decyl alcohol group produced by hydrolysis of an alkoxy group in an organoalkoxysilane and (B) a bond with a ruthenium atom in an organopolyoxane containing a hydrogen atom bonded to a ruthenium atom. a condensation reaction between hydrogen atoms. As the (c) condensation reaction catalyst, one type of condensation reaction catalyst may be used alone, and two or more types of condensation reaction catalysts may be used in combination as needed. The type of the (C) condensation reaction catalyst is not limited as long as a hard coating film can be formed; t. As the above (c) condensation reaction _, for example, 163665.doc •10·201247802, zinc m or an iron-based catalyst is used. As the zinc, tin, turmeric, agglomerated or iron-based catalyst, an organic acid metal salt is preferred, and as the organic acid, a fatty acid is preferred. Specific examples of the above-mentioned (C) hardening_ are zinc diacetate, dioctanoic acid, zinc octoate, zinc di neodecanoate, zinc undecolate, and zinc dimercapto acrylate; Neodecanoic acid dif-butyltin, = dibutyltin acetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxide, tin dioctoate-laurel Tin, tin acetate, tin tetraacetate, dibutyltin oxide, dibutyltin benzyl succinate, dibutyltin bis(triethoxydecyloxy), diphenyltin diacetate, tin octoate, neodymium Di-n-butyltin acid; diacetic acid, octanoic acid, octanoic acid; diacetic acid, dioctanoic acid, octanoic acid; iron diacetate, iron dioctoate and iron octoate. In the composition for forming a coating film of the present invention, the amount of the (c) condensation reaction catalyst is not limited to be '0.01 to 8 by mass based on the total mass of the solid content of the composition for forming a coating film. %, more preferably 〇 quality 0/. More preferably, it is 1 to 3 mass%. The composition for forming a coating film of the present invention preferably further comprises (D) a silicone resin. The coating film-forming composition of the present invention comprising the above (D) oxime resin can form a coating film having a more uniform thickness and a dense thickness. Therefore, the coating film-forming composition of the present invention containing the partially hydrolyzed condensate of the above (D) oxime resin can form a coating film which is more excellent in terms of rust resistance and the like. The (D) oxime resin may include a trifunctional fluorinated oxygen unit (hereinafter referred to as a T unit) represented by a unit formula (Resi 〇 3/2), and a unit formula (Re2Si02/2) as needed. The DT type of the monofunctional oxirane unit (hereinafter referred to as d 163665.doc 201247802 兀) and the monofunctional oxirane unit (hereinafter referred to as Μ unit) shown by the unit formula (R^SiOm) Or MDT type oxime resin; a tetrafunctional oxirane unit represented by a unit (siOw) (hereinafter referred to as q unit = unit MQ resin. In the above formula, RC independently represents a monovalent smoky group. ^ is: The valence hydrocarbon group 'is exemplified by (4) the same group... a small amount of "alkoxy group represented by 〇Rb or hydroxy (D) oxirane resin may be solid or liquid at normal temperature" in the case of a solid state In addition, it is also possible to have a bright point. Among them, it is preferably the one shown in the following average unit formula (2). [R Sl〇3/2]a[R7R8pSi〇(3.p)/2]b (2) { Wherein 'R and R are each independently a monovalent hydrocarbon group, and the sizing 8 is independently an alkoxy group or a meridine group, wherein 7 〇 mol% or more of R8 is a number of morphologies p is Μ Ρ < , a is G or Number, b is a positive number, and b/(a+b^1.0} is selected. The above (D) average monovalent formula (2) is preferably a partially hydrolyzed condensate of an organic alkoxylated stone. There is no limitation as long as it is a partially hydrolyzed condensate of an organic alkoxy group having a lanoxy group. As a partially hydrolyzed condensate of an organoalkoxy decane, one type of organic alkane U knives may be used alone to hydrolyze the condensate. 'A partial hydrolyzed condensate of two or more kinds of organic alkoxy saponins may be used in combination as needed. The definition and exemplification of the one-valent smoky group in the above average unit formula (2) are as described above. The above-mentioned (D) oxirane resin is preferably one molecule in the above-mentioned (D) oxirane resin, which is preferably a methyl group or an ethyl group, an ethyl group or an aryl group. It has at least one alkenyl group 16366S.doc -12, 201247802. The alkenyl group in this case is preferably a vinyl group. The alkoxy group in the above average unit formula (2) is a carbon number 丨~"'. The linear alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, specifically, a methoxy group or a Oxyl, propoxy, etc. More preferably decyloxy or ethoxy, more preferably methoxy. In the above average unit formula (2), preferably 3 $ a + b S 1 〇〇, More preferably, it is 4 ga+b^50, and more preferably 5^a+b^2〇. The compounding amount of the above (D) oxime resin in the composition for forming a coating film of the present invention is not limited, and is The mass of the solid content of the composition for forming a film is preferably from 5 to 80% by mass, more preferably from 10 to 50% by mass, still more preferably from 15 to 43% by mass. The composition for forming a coating film of the present invention may further comprise (E) a hydrogenation reaction catalyst. In particular, when the composition for forming a coating film of the present invention contains the above (D) oxime resin, and particularly when the (D) oxime resin contains an alkenyl group, it is preferable to further contain (£) 矽Hydrogenation catalyst. As the (E) ruthenium hydrogenation catalyst, a ruthenium hydrogenation reaction catalyst can be used alone, and two or more kinds of ruthenium hydrogenation catalysts can be used in combination as needed. As the (E) hydrazine hydrogenation catalyst, a compound known as a ruthenium hydrogenation catalyst such as platinum, rhodium, ruthenium, palladium, starvation or ruthenium can be used. In particular, platinum catalysts are more useful. Examples of the platinum-based catalyst include a gas platinum acid, a platinum monomer, and a solid platinum supported on a carrier such as alumina, ceria or carbon black, a platinum-vinyl siloxane complex, and platinum. _phosphine complex, platinum-phosphite complex, alcohol platinum catalyst, and the like. In the case of the hydrazine hydrogenation reaction, the platinum-based catalyst is used in the form of platinum, and the total solid content of the composition for forming a coating film is 163,665.doc •13·201247802 based on the amount of 〇.〇〇〇〇1 Mass % ~ 〇 "% by mass". The composition for forming a coating film of the present invention can be prepared, for example, by mixing the above components (A) to (C) and optionally the components (D) and/or (E) and further optional components with a solvent. . The type of the optional component is not particularly limited as long as it does not interfere with the effect of the water-repellent coating film obtained, and examples thereof include a pigment, a dye, a preservative, a bactericide, an anti-aging agent, and an anti-corrosion agent. Rust inhibitor, antistatic agent, flame retardant, antifouling agent, etc. Examples of the solvent include aromatic hydrocarbon compounds such as benzene, toluene, and diphenylbenzene, and compounds such as diethylamine, diisopropyl ether, and tetrahydrocarbamate; methanol, ethanol, propanol, butanol, and An alcohol compound such as an alcohol; a ketone compound such as acetone, methyl ethyl ketone or decyl isobutyl ketone; an ester compound such as ethyl acetate or butyl acetate; a functionalized hydrocarbon compound such as a gas, a tri-ethylene or a tetra-gasified carbon; a saturated hydrocarbon compound such as n-hexane, n-octane, isooctane or octadecane; trimethyl methoxy decane, dimercapto dimethoxy decane, methyl trimethoxy decane tetraethoxy decane, etc. a volatile polyoxosiloxane such as a decane compound or a hexamethylene dioxane, but is not limited thereto. Further, the solvent may be used singly or in combination of two or more. The amount of the solvent to be used in the composition for forming a coating film of the present invention is not particularly limited, and is preferably 50 98% by mass, and more preferably 7 to 95% by mass based on the total mass of the composition for forming a coating film. And further preferably ~ column quality %. In other words, the solid material forming blade in the composition for forming a coating film of the present invention preferably has a mass of 2 to 50 by mass based on the total mass of the composition for forming a coating film. More preferably, it is 5 to 3 % by mass, and still more preferably ~ mass 163665.doc 201247802 %» The composition for forming a coating film of the present invention can be cured by heating to form a water-repellent coating film. . Therefore, in the method for forming a coating film of the present invention, the composition for forming a coating film is applied to the surface of the substrate and then heated to form a water repellency having high hydrophobicity and sufficient water repellency. Laminating. The material of the substrate is arbitrary, and may be metal, metal oxide, glass, ceramic, plastic, rubber, etc., but in terms of heat resistance, at least the surface of the substrate (preferably the entire substrate) contains metal, metal oxide. Inorganic materials such as materials, glass and ceramics. Examples of the metal include iron, aluminum, copper, gold, silver, brass, tin, nickel, and stainless steel. Furthermore, various mineral deposits can be applied to the metal surface. The surface of the substrate may also include a coating film containing ruthenium. The coating film containing ruthenium is preferably a polyoxygenated hard coating film. The polyoxygen hardening coating film can be obtained by a known curing mechanism such as a condensation reaction curing type, a hydrogenation reaction hardening type, an organic peroxide curing type, and an ultraviolet curing type. The condensation reaction-hardening type polyoxygen hardening coating film can be obtained, for example, by hardening a curable polyanthracene composition containing the following: (1) liquid at normal temperature and molecular chain terminal by stanol group or a partially hydrolyzed condensate of a hydrolyzable group blocked with a hydrazine atom, or a partially hydrolyzed condensate of an organic decane having a hydrolyzable group bonded to a hydrazine atom, (7) an amount sufficient to crosslink the component (1) and (d) A sub-bonded hydrolyzable organic decane-based or organosiloxane-based cross-linking agent, and I63665.doc 15· 201247802 (3) The required amount of condensation reaction promotes catalyst β as a dream in (1) The hydrolyzable group of the atomic bond may, for example, be a ketone oxime group (sometimes called ketoximino) such as a methyl ketone oxime group or a methyl ethyl ketone oxime group; General formula: _〇_n=cr9rig (wherein R9 and Ri〇 are the same or different alkyl groups, preferably an alkyl group having 1 to 6 carbon atoms)]; oxy group, ethoxy group Alkoxy group; anthraceneoxy group such as ethoxycarbonyl; alkylamine group such as N-butylamino group, N,N-diethylamino group; ν·methylethylammonium group Acyl group; Ν, Ν_ diethylamine group and the like Ν, Ν- dialkyl amine group; (iv) propan-yl group material. Preferably, the oxime is a silk group and a ruthenium group 0 as the component (1). Specifically, it can be exemplified that the both ends of the molecular bond are blocked by a sulfoxide group or a methoxy group or an ethoxy group bonded to a ruthenium atom. Dimethyl polyoxyalkylene, methyl alkyl polyoxyalkylene, dimethyl methoxy oxane-methyl phenyl oxime, polymer fluorenyl (3, 3, 3 · tri-propyl) Shixi Oxygen Burning or Oxygen Oxide Burning = Sub-hydrolysis Condensate, etc. 'But in terms of the properties and economics of the hardened material. It is preferably a partial hydrolysis of methyl polyoxane or alkoxy decane. Things. Further, it is a terminal group of a -methyl polyoxyalkylene which is blocked by a decyloxy group or an ethoxy group bonded to a ruthenium atom, and is exemplified by methyl dimethoxy decyloxy 'methyl diethoxy oxalate Ethyloxy, trimethoxy, alkoxy, triethoxyoxy,? Base: methoxy(tetra)ylethyl(:methyl)nicoxy, dimethoxydecylalkylethyl(dimethyl)decyloxy and the like. As the component (1), two or more kinds of diorganopolysites or organic stones can be used in combination. The hydrazine is hydrolyzed. For example, 丨(1) 饥 之 之 之 〇 〇〇 〇〇 〇〇 之 之 之 之 之 之 之 之 之 分子 分子 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 163 The viscosity of the looo~5〇〇〇mpa s molecular bond at both ends is a mixture of the dimethyl polyoxan closed by the Shixiyuan alcohol group. Here, the blending of the component (M) and the component (1-2) is preferably in the case of a mass ratio of (10) to 卜. In this case, the viscosity of the component (1) is less than 1000 to less than 5000 mPa. s, coatability good. (2) The crosslinking agent having the component (1) has at least two hydrolyzable groups bonded to a ruthenium atom, and preferably has three or four hydrolyzable groups bonded to a ruthenium atom. Representatively, it is represented by the formula: RnySiX4_y (wherein r11 is a hydrocarbon group having 1 to 10 carbon atoms, X is a hydrolyzable group bonded to a ruthenium atom, and y is 0 or 1). Or an organic oxirane oligomer which is a partially hydrolyzed condensate of the organic mash. Further, the definition and exemplification of the monovalent hydrocarbon group and the hydrolyzable group bonded to the ruthenium atom are as described above. The (2) component may, for example, be tetradecyloxydecane, tetraethoxydecane, n-propyl n-decanoate, methyltrimethoxydecane, mercaptotriethoxydecane or dimethylform. Oxy decane, dimethyl diethoxy decane, vinyl dimethoxy decane, vinyl tris(2-methoxyethoxy) decane, decyl propyl triethoxy decane, 3-shrink Glyceroxypropylmethyldimethoxycarbazide, bis-[3-(diethoxycarboyl)-propyl]tetrasulfide bond, bis-[3_(triethoxydecyl)-propyl Disulfide, triethoxydecyl propyl methacrylate monosulfide, tetrakis(decylethyl ketoxime) decane, methyl tris(methyl ethyl ketoxime) decane, vinyl tris Ethyl ketone oxime) decane, decyltriethoxy decane, ethyltriethoxy decane, methyl triisopropoxy decane tetraisopropenyloxy decane, methyl tris(N, N_ II Ethylamino) decane. (2) The amount of the component is sufficient to harden the (丨) component. When the hardenability is 163665.doc: • 17- 201247802, the polyoxo oxygen composition is a single liquid type, so that the moisture can be blocked. The amount that can be stored for a long time and hardened at room temperature when exposed to moisture, usually 2 to 30 mass. /. The scope. Specifically, the compounding amount of the component (2) is, for example, 5 to 1 part by mass based on the mass component of the component (1), and is preferably 8 to 40 parts by mass in terms of hardenability. range. As (3), a conventionally known condensation reaction promoting catalyst can be used. Specific examples thereof include dibutyltin acetate, dibutyltin dioctanate, dibutyltin, dilauric m-dibutyluccinate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate, and the like. Organotin compound; tetrakis(isopropyl) titanate tetrakis(n-butyl) titanate, dibutoxy bis(acetoxime) titanium, triisostearate isopropyl titanate, tri Dioctyl-based oxy-enriched isopropyl vinegar, bis(dioctylpyroxyloxy)-organic titanate compound such as acetic acid phthalate; tetrabutyl phthalate, tetrakis(acetonitrile) Occurrence, 鍅i tetraisobutyl g曰, butoxy bis(acetonitrile) hydrazine, bismuth naphthenate and other organic recording. Organic compounds such as di-(ethyl ethyl acetate), tris (ethyl g-acetone), etc.; zinc acid, ring-burning acid, octanoic acid, organic acid metal | amineamine, ethanolamine, diethanolamine, etc. Media. Further, the organotin compound or the organic (IV) g-based compound is suitable for a dealcoholization type condensation-reacting polyclay composition, and the organic titanate compound is suitable for a decondensation-type condensation-reaction-hardenable polyoxyl composition. (3) The amount of the component to be added is an amount sufficient to promote the condensation reaction of the component (1) and the component (7), and is, for example, G, 1 to 15% by mass, preferably 1/4% by weight. When it is based on the component (1), for example, it is (U 2 2 parts by mass), and in terms of hardenability, it is preferably in the range of 丨 12 parts by mass. 163665.doc 201247802 The reaction-hardening type polyoxygen hardening coating film can be obtained, for example, by heat-hardening a hardened r-site polyoxo-oxygen composition: & 1 molecule, and up to 2 and a stone atom bond The second base of the knot has at least 2, preferably at least 2, gems of octagonal oxygen (for example, a dimethyl polyoxan's ketone with both ends blocked by dimethyl ethoxylate). It is an organopolyoxane having three or more hydrogen atoms bonded to the Shixi atom (for example, a methyl hydrogen polysulfide blocked by a trimethyldecyloxy group at both ends), and a hydrogenation catalyst (such as gas) And preferably further comprising a hydrazine hydrogenation reaction inhibitor. The polyoxygen hardening coating film which is an organic peroxide curing type can be, for example, a diorganopoly group having at least 2 alkenyl groups in the knives 1 knives. A hardening polyoxyl composition such as a decane or an organic peroxy oxime is heated and hardened. The ultraviolet curable polyoxygen hardening coating film can be obtained, for example, by hardening a curable polyoxynitride composition comprising: (4) hydrogenation reaction hardening type organic polyphenylene oxide; and a photopolymerization initiator (b) an acrylic acid-functional polyoxophane and a photopolymerization initiator, or (4) an epoxy-functional organic oxide plant and a cation-generating catalyst. The photopolymerization initiator can be irradiated from the prior A compound which generates a radical by ultraviolet rays, such as an organic peroxide 'carbonyl compound, an organic sulfur compound, an azo compound, etc., is suitably selected. Further, a cation-generating type catalyst can be a well-known sulfonium salt, specifically a triaryl group. It is suitably selected from the group consisting of salt-dissolving, triarylsulfonium salt, bis(dodecylphenyl)hexafluoroantimonate, etc. The above-mentioned ultraviolet curable type of hardenable polyoxynoxy composition is at a temperature of 〇8-8〇 left== When the ultraviolet ray is irradiated as follows, a hardened coating film can be formed, and the wavelength region of the ultraviolet ray is preferably fine to a full nm, and particularly preferably 200 when a cation is produced using a cation 163665.doc -19·201247802. The range of 300 nm is preferably in the range of 300 to 400 nm in the case of using a hydrogenation-type organopolyoxane. The composition for forming a film of the present invention can be applied to a surface of a substrate. The method of application can be carried out by a dipping method, an impregnation method, a roll coating method, a flow coating method, a brush coating method, a spray method, etc. The thickness of the coating film formed on the surface of the substrate is not particularly limited. However, in terms of thermal conductivity, it is preferably a thickness of 0.1 to 5.0 μηι, more preferably 丨〇 2 2 μπ 2 thickness. The above heating may be carried out, for example, at a temperature of 100 to 30 Torr, preferably 120 to 250 °. The temperature range of C is more preferably in the range of 13 〇 to 2 〇〇〇 c. The heating time is not limited, and for example, it can be heated within a time range of i minutes to 丨 hours. Preferably, the substrate coated with the coating film-forming composition is placed at a temperature of 40 C or less, preferably at room temperature, before volatilization to volatilize the solvent. [Industrial Applicability] The composition for forming a coating film and the method for forming a coating film of the present invention can be preferably used for various substrates requiring excellent water repellency, for example, for use in a gas containing water vapor and Surface treatment of any substrate with a surface that has the potential for condensation and/or frosting. As such a substrate, for example, a so-called water-use product such as a kitchen, a bathroom, or a bathroom can be cited. Since the base body of the present invention has a water-repellent surface having high hydrophobicity and sufficient water-skiing performance, it can be preferably used for hot-heating of the hot air with the external air, specifically for heat dissipation. body. It is particularly preferable to use the substrate of the present invention as a cooling fin comprising a plurality of cooling fins arranged in parallel at regular intervals and a heat exchanger connecting the heat exchange tubes of the fins. I63665.doc -20- 201247802 Further, the above heat exchanger is more preferably an air blower. In the present invention, it is preferable to use a freezing device or a refrigerating device such as a box, or an air conditioning device such as ice or air conditioner which is used in a humid environment. Implementing you] 丞 狍 狍 及 及 及 and comparison examples. . The present invention is described in detail, but the present invention is not limited by the embodiments. Further, the rolling angles in the examples and the comparative examples were carried out in the following manner, and the methyltrimethoxydecane partial hydrolysis condensate and the 2 series were evaluated in the following manner: [rolling angle (sliding angle) Angle)] Using a contact angle meter (manufactured by Kyowa Interface Science, DM_7〇〇) and using the slip method to perform 骇. Specifically, 'with 2 μl of water droplets, the surface is tilted with the surface of the droplet, and the surface is observed by the camera, and the angle of inclination at which the end point and the back end of the water droplet start to move is taken as the roll. Angle (slipping angle) 〇 [Preparation of thiol trimethoxy decane partial hydrolysis condensate 1] Into a four-necked flask of 5 〇〇 ml equipped with a stirring device, a cooling tube and a thermometer, decyltrimethoxy decane 259.6 was charged. g, 28.6 g of methanol and 0.13 g of trifluoromethane acid were uniformly mixed, 29.6 g of water was dropped, and the mixture was reacted at a reflux temperature of decyl alcohol for 1 hour, and the reaction was carried out while removing methanol at a temperature of 120 ° C under normal pressure. 3 hours. After cooling to room temperature, ammonia gas was blown in to neutralize, and then stripped at a temperature of 80 ° C and a reduced pressure of 5 〇 mmHg, followed by filtration to obtain a methyltrimethoxy decane partial hydrolysis condensate. i. From the results of 13C NMR and 29Si NMR, it was confirmed that the obtained 163665.doc -21 · 201247802-based dimethoxy group; the epsilon-oxide partial hydrolysis condensate 1 had the following average composition formula β [CH3Si03/2] 3 8 [CH3R3丨3Si〇丨7/Mountain 5 (wherein R3 is a methoxy group). [Preparation of methyltrimethoxydecane partial hydrolysis condensate 2] Into a four-necked flask equipped with a stirrer, a cooling tube and a thermometer, ruthenium trimethoxy decane 265 1 g, 曱After 23 3 g of alcohol and 0.13 g of trifluoromethane acid were uniformly mixed, 24 9 g of water was dropped, and the mixture was reacted at a reflux temperature of decyl alcohol for 1 hour, and the methanol was removed at a temperature of 12 〇eC under normal pressure. It reacted for 3 hours. After cooling to room temperature, ammonia gas was blown in and neutralized. Further, stripping was carried out at a temperature of 80 ° C and a reduced pressure of 50 mmHg, followed by filtration to obtain a mercaptotrimethoxydecane partial hydrolysis condensate 2. As a result of measurement by 13C NMR and 29Si NMR, it was confirmed that the obtained methyltrimethoxydecane partial hydrolysis condensate 2 had the following average composition formula. [CH3Si〇3/2]〇.3[CH3R3i.3Si017/2]3.0 (wherein R3 is a methoxy group). [Examples 1 to 16 and Comparative Examples 1 to 2] The components shown in Tables 1 to 3 were uniformly mixed in the mass parts shown in Tables 1 to 3 to prepare Examples 1 to 14 and Comparative Examples 1 to 2 The composition for forming a coating film. In addition, the initial catalyst was prepared so that the amount of platinum metal was 10 ppm of the solid content of the composition for forming a coating film. Then, after being degreased in the degreasing degreasing agent, the aluminum test panel (ΠS A1050P) which was washed with running water and distilled water and dried by heating was immersed in the above composition and pulled up to thereby be The film forming composition was coated on the surface of the above test panel. The above-mentioned coated test panel was placed at room temperature for several times 163665.doc -22·201247802 'after volatilization of isooctane' was heated at 2 ° C for 20 minutes to form a hydrophobic hardening on the surface of the above test panel. Covered film. The roll angle (slip angle) on the thus obtained hydrophobic hard coating film was measured. The results are shown together in Tables 1 to 3. The meanings of MH and D in the table are as follows. MH: indicates that (H(CH3)2Si〇1/2) unit D· indicates that ((CHshSiO2, 2) unit' subscript indicates £> the average number of bonds of the unit and 'the methyl phthalate in the table is Mitsubishi Chemical Corporation The manufactured product name is MKC Silicate MS56 (the average number of ruthenium atoms in the molecule is about 1 )). Further, the MQ resin in the table is the following average unit: [(CH3)3 Si〇i/2] 0.44 [ The oxime resin represented by Si〇4/2] 0.56 has a weight average molecular weight of about 4,600 in terms of standard polystyrene obtained by gel permeation chromatography, and contains about 3 wt% of a hydroxyl group. 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Methyltrimethoxy oxacyclohexane 5.83 6.90 5.60 4.50 4.20 5.60 5.83 0.34 0.67 0.67 0.67 0.67 0.67 0.34 Methyltrimethoxydecane Partially hydrolyzed condensate 1 2.91 1.50 2.80 3.90 4.20 2.80 Methyl decanoate - - - - 2.91 Dimethyltin neodecanoate "0.18 0.18 0.18 0.18 0.18 0.18 "0.18 isooctane 91 91 91 91 91 91 91 Rolling angle ( Slip angle) 5 5 5 7 13 5 6 163665.doc • 23- 201247802 [Table 2] Example 8 Example 9 Implementation 10 Example 11 Example 12 Example 13 Methyltrimethoxydecane - - 7.89 5.71 3.81 3.81 Vinyltrimethoxydecane 5.60 5.52 - - - - MmD98Mh 0.67 1.18 1.18 3.36 3.36 3.36 Partial hydrolysis of methyltrimethoxydecane Condensate 1 2.80 2.37 - - 1.90 - MQ Resin - - - - - 1.90 Neomethyl phthalate 0.18 0.18 0.18 0.18 0.18 0.18 Platinum Catalyst 10 ppm - - - Surface Isooctane 91 91 91 91 91 91 Roll Falling angle (slipping angle) 6 6 6 4 5 15 [Table 3] Example 14 Example 15 Example 16 Comparative Example 1 Comparative Example 2 Methyltrimethoxy decane 5.60 5.26 3.95 - - Vinyl trimethoxy decane 5.60 5.52 - - - mhd98mh 0.67 1.18 1.18 0.67 0.67 Mercaptotrimethoxydecane partial hydrolysis condensate 1 - - Discussion 8.40 7.89 Mercapto tridecyloxydecane partial hydrolysis condensate 2 2.80 2.63 3.95 - - Neodecanoic acid dimethyl Tin 0.18 0.18 0.18 0.18 0.18 isooctane 91 91 91 91 91 Rolling angle (slipping angle) 4 4 4 33 18 According to the results of Examples 1 to 14 and Comparative Examples 1 and 2, it is understood that the coating film forming combination of the present invention The material can form water with good water-skiing performance The hardening is coated, and on the other hand, in the absence of the organoalkoxydecane, the water repellency of the hardened coating obtained is lowered and the water slidability is deteriorated. 163665.doc 24-